Dichloro-methyl-antraquinones and process of making same



Patented Feb.- 28; 1 933,

UNITED 'srAi-ras: ioFFic o'rro BAYER, or FRANKFORT+ON-THE-MAIN; e aia A NY," assmnon 'ro' GENERAL ANILINE woaxs, moi, orimw YORK, N. Y.,' Aconromrmir or DELAWARE,

DIGHLORO-METHYL-ANTRAQUI;NONES mwnraocass or MAKING: smn

No Drawing. Applicationflle'd February 17, 1931; Serial No, 516,505; and in Germany February 22, 1980.

My present invention relates to dichloromethyl-anthr-aquinones and process of making same.

This process comprises introducing gaseous Chlorine intoa solution containing sulfuric acid and 2-methyl-anthraquinone untila test shows that 2 atomic proportions of chlorine have been absorbed; i. e. introducingat least 2 molecularproportions of chlorine. The sulfuric acid solution used may contain sulfuric acid anhydride or also diluents aswater or acetic, acid; Chlorine carriers as iodine or antimony pentachloride may be further added.i The chlorination .is

"carried out at a temperature ranging from room temperature up to 150, advantageously at about 70 till above 100.

Thereby a mixture of isomeric dichloromethyl-anthraquinones is obtained contain 'ing probably as main portions 1.5-and 1.8-

dichloro 2-methyl-anthraquinone of the for mulae: I v v or o CH| OH;

- and Nearly the same mixture of dichloro methyl-anthraquinones is obtained by carrying out thechlorination in two steps At first l-methyl-anthr-aquinone is convertedine to ll-chloro-2-methyl-anthraquinone for instance in the manner described in German Patent No. 269,249 and its addition 'No. 293,156 and the formed 1-chloro-2 methyl-anthraquinone (in a pureor-crude form) is ready been treated with chlorine in a sulfuricacid'solution (Ur S. Patent1,504,164

Such an introduction is 1 a surprising fact; there was much more to be expected (la-chloromethyl-derivatives since the hydrogen atoms of the methyl group are known to be easily replaced by halogen (see U.- S. Patent No;

In order to further illustrate my inven-. tion the following examples are given the parts being by weight and. alltemperatures in centigrade degrees; but I wish to beun derstood that my inventio n is not limited to the; examples given, nor to theexacticonditionsstated therein.

Example 1 i Into a'solution of 50 parts of 2-methylanthraquinone and 0.3 parts of iodine in 500 parts of sulfuric acid monohydrate and 30 parts of fuming sulfuric acid of SO chlorine is introduced as about 100 while stirring until an increase in weight of 16.0-16.5 parts, or until the anthraquinone compound contains MB-24.8% chlorine. Then the reaction product is fractionally precipitated from the sulfuric acid solution by a gradual addition of water. product thus obtained represents light'yellowish crystals soluble, in organic solvents, it sinters ate130 and melts at 135%140". This product or also'the sulfuric acid reaction mass may be immediately used for further transformation processes. I Example 2 2-methyl-anthraquinone is treated with sulfuryl in German Patent No. 269,249. 50 parts of The crude chloride, in the manner described the crude 1-chloro-2 methyl-anthraquinonethus. obtained and 0.2. partsof iodine are dis-- solved in 300'parts of fuming sulfuric acid of S0 Into, this solution containing 3% gaseous chlorine is'introduced at 70? until one atomic proportion of chlorine has been absorbed. The reaction mass is further treated according to Example 1. The product thus obtained is nearly identical to that of Example 1.

, Example 5 50 parts of Q-methyl-ahthraquinorie are dissolved in 400 parts of sulfuric acid of strength and chlorine is introduced at about; U while an increased surface of the mass is maintained for instance by stirring. The introduction is interrupted When 2 atomic amounts of chlorine have been absorbed. In

J, oontradisc'tinction to the foregoing examples and 01 I o r i which articles represent light yellowish crystals soluble in organic solvents, sintering at 123130 and melting at l40. i In testimony whereof, I aflix my si nature.

OTTO BA BB. 

